Carboxylic acid salts of the condensation product of epihalohydrin and an aliphatic amine



Unite 3,d%,7% Patented May 21, 1%63 CARBOXYLIC ACE fiAL'iS {3F TEECGNDENSA- TION PRODUCT F EPIHALOHYBRZN AND AN ALHHATIC Ali/ENE Henryk A.Cyba, Chicago, llh, assignor to Universal (Bil Products Company, DesPlaines, 11., a corporation of Delaware N0 Drawing. (Briginaiapplication May 23, 1958, Ser. No. 737,211. Divided and this applicationAug. 11, 1960, Ser. No. 48,812

6 Claims. (Cl. Zed-494.5)

This is a division of my copending application Serial No. 737,211, filedMay 23, 1958, now Patent No. 3,017,- 360, January 16, 1962, and relatesto a novel composition of matter which is particularly suitable for usein improving hydrocarbon oil in a number of important properties.

During processing, transportation, storage and/or use, hydrocarbon oilsgenerally deteriorate, particularly when subjected to elevatedtemperature. For example, hydrocarbon oil being subjected tofractionation or conversion is first heated to an elevated temperature.Such heating may be effected in an externally fired furnace or it may beaccomplished by heat exchange with a hotter fluid. In the first case,the hydrocarbon fluid is passed through tubes during such heating and,in many cases, deposit formation occurs in the tubes and results in lossof eflicient heating and/or plugging of the furnace tubes. in heatexchange systems the hydrocarbon oil is passed either through tubesdisposed in a shell or through the shell surrounding the tubes. Duringheating of the oil, deposit formation occurs either within the tubes orin the hotter sections of the shell, with the result of decreasedefliciency in heat transfer and even in plugging of the tubes. Anotherexample in which hydrocarbon oil is passed in heat exchange is in thecase of jet fuel, where the jet fuel is passed in heat exchange with thehot exhaust gases, both to cool the exhaust gases andto heat theincoming fuel. Temperatures as high as 500 F. or more are encounteredfor at least short periods of time, with the result that depositformation occurs and either plugs the heat exchanger or interferes withelficient heat transfer.

Other examples where instability of the hydrocarbon oil is a problem arehydrocarbon oils heavier than gasoline including diesel oil, heateroils, burner oils, range oils, fuel oils, transformer oils, hydraulicoils, slushing oils, etc. Deposit formation in these oils isobjectionable because it results in plugging of filters, strainers,burner tips, injectors, etc., reduction in viscosity and accordingly inflowing properties, as well as the formation of varnish and sludge inthe diesel engine. In addition to preventing hese objectionable depositformations, the novel additive i the present invention also functions toretard corrosion of metal surfaces in contact with hydrocarbon oil andwater. It is well known that water generally is present in hydrocarbonoils and results in corrosion of piping, pumps, shells, fractionators,receivers, storage tanks, etc., as well as internal equipment such asbafile plates, bubble trays, bubble caps, etc.

in addition to serving the important functions hereinbefore set forth,the novel additive of the present invention also serves to lower thepour point of the hydrocarbon oil. This is of advantage in the case ofheavier oils which are being pumped and also of particular advantage inthe case of lubricating oils, gas turbine oils, steam turbine oils, jetturbine oils, marine oils, etc. in order that the oil retain its flowingproperties at lower temperatures. In addition to reducing pour point andlowering the cold test, the additive also improves the viscosity indexof lubricating oil.

The additive of the present invention also serves an important functionin the case of gasoline or naphtha. As hereinbefore set forth, theadditive serves as a corrosion inhibitor and therefore reduces corrosionproblems during handling of the gasoline.

From the above description, it will be noted that the novel additive ofthe present invention serves to improve hydrocarbon oil in a number ofdifferent ways. The hydrocarbon oil includes gasoline, naphtha, jetfuel, kerose e, burner oil, heater oil, range oil, gas oil, fuel oil,lubricating oil, residual oil, etc. As hereinbefore set forth, theadditive may be incorporated in the oil prior to heating for furtherprocessing, or it may be incorporated in the oil after such treatment.

In one embodiment the present invention relates to a method of improvinga hydrocarbon oil which comprises incorporating therein a stabilizingconcentration of a carboxylic acid salt of the condensation product ofan epihalohydrin compound with an amino compound having at least 12carbon atoms.

In a specific embodiment the present invention relates to a method ofpreventing deposit formation in a heat exchanger through which twofluids at diiferent temperatures are passed which comprisesincorporating in at least one of said fluids, in an amount suilicient toprevent deposit formation, a salt of a dibasic carboxylic acidcontaining from about 6 to about carbon atoms per molecule and thecondensation product of epichlorohydrin with an amine compound havingfrom about 12 to about 40 carbon atoms per molecule.

In still another embodiment the present invention relates to a method ofimproving burner oil which comprises incorporating therein a stabilizingconcentration of an oleic acid salt of the condensation product ofepichlorohydrin and tallow amine.

In still another embodiment the present invention relates to hydrocarbonoil containing a stabilizing concen tration of the novel additive hereinset forth.

The novel additives of the present invention also are new compositionsof matter and are being so claimed in the present application.

As hereinbefore set forth, the novel additive of the present inventionis a carboxylic acid salt of the condensation product of anepihalohydrin compound with an amine compound having at least 12 carbonatoms. The amine compound used in preparing the reaction productcontains at least 12 carbon atoms and preferably at least 15 carbonatoms. Generally the total number of carbon atoms in the amine will notexceed about 40 carbon atoms per molecule. In a preferred embodiment theamine contains a straight chain of at least 3 carbon atoms attached tothe nitrogen atom. In this preferred embodiment, the alkyl groupattached to the nitrogen atom is of normal configuration and notsecondary, tertiary or of cyclic configuration. However, the alkyl groupmay contain branching in the chain, provided such branching occurs onthe fourth carbon atom from the nitrogen atom or further distanttherefrom.

Any suitable alkyl amine meeting the requirements set forth herein maybe used in preparing the additive of.

the present invention. In addition to the above requirements, it isessential that the alkyl amine is a primary or secondary amine; that is,only one or two of the hydrogen atoms attached to the nitrogen atom aresubstituted by alkyl groups. Tertiary amines (no hydrogen atom attachedto the nitrogen atom) cannot be used in the present invention. It isunderstood that the term alkyl amine is used in the presentspecifications and clairns to include primary alkyl amines, secondaryalkyl amines, polyamines, N-alkyl polyamines, N,N'-dia1kyl polyamines,etc., all of which meet the requirements hereinbefore set forth.

Illustrative examples of primary alkyl amines include dodecyl amine,tridecyl amine, tetradecyl amine, pentadecyl amine,.hexadecy1 amine,heptadecyl amine, octadecyl amine, nonadecyl amine, eicosyl amine,heneicosyl amine, docosyl amine, tricosyl amine, tetracosyl amine,pentacosyl amine, hexacosyl amine, heptacosyl amine, octacosyl amine,nonacosyl amine, triacontyl amine, hentriacontyl amine, dotriacontylamine, tritriacontyl amine, tetratn'acontyl amine, pentatriacontylamine, lhexatriacontyl amine, heptatriacontyl amine, octatriacontylamine, nonatriacontyl amine, tetracontyl amine, etc. Conveniently thelong chain amines are prepared from fatty acids or more particularlyfrom mixtures of fatty acids formed as products or by-products. Suchmixtures are available commercially, generally at lower prices and, asanother advantage of the present invention, the mixtures may be usedWithout the necessity of separating individual amines in pure state.

An example of such a mixture is hydrogenated talloW amine which isavailable under various trade names including Alamine H261) and ArmeenHTD. These products comprise mixtures predominating in alkyl aminescontaining 16 to 18 carbon atoms per alkyl group, although they containa small amount of alkyl groups having 14 carbon atoms, and also meet theother requirements hereinbefore set forth.

Illustrative examples of secondary amines include di- (dodecyl) amine,di-(tridecyl) amine, di-(tetradecyl) amine; di-(pentadecyl) amine,di-(hexadecyl) amine, di- (heptadecyl) amine, di-(octadecyl) amine,di-(nonadecyl) amine, di-(eicosyl) amine, etc. In aother embodiment,which is not necessarily equivalent, the secondary amine Will contain.one alkyl group having at least 12 carbon atoms and another alkyl grouphaving less than 12 carbon atoms, both of the alkyl groups having astraight chain of at least 3 carbon atoms attached to the nitrogen atom.Illustrative examples of such compounds include N-propyl-dodecyl amine,N-butyl-dodecyl amine, N-amyl-dode'cyl amine, N-butyl-tridecyl amine,N-amyltridecyl amine, etc. Here again, mixtures of secondary amines areavailable commercially, usually at a lower price, and such mixtures maybe used in accordance with the present invention, provided that theamines meet the requirements hereinbefore set forth. An example or" sucha mixture available commercially is Armeen 2HT which consists primarilyof dioctadecyl amine and dihexadecyl amine.

Preferred examples of N-alkyl polyamines compriseN-alkyl-1,3-diaminopropanes in which the alkyl group contains at least12 carbon atoms. Illustrative examples include N-dodecyl-1,3-diaminopropane, N-tridecyl-1,3-diaminopropane,N-tetradecyl-l,3-diaminopropane, N-pentadecyl-l,3-diaminopropane, N-hexadecyl-1,3-diaminopropane, N-heptadecyl-1,3-diaminopropane,N-octadecyl-1,3- diaminopro'pane, N-nohadecyl-l,3-diaminopropane, N-eicosyl-1,3-diaminopropane, N-heneicosyl-l,3 diaminopropane,N-docosyl-l,3-diaminopropane, N-tricosyllfidiaminopropane,N-tetracosyl-l,3-diaminopropane, N- pentacosyl-l,3-diaminopropane,N-hexacosyl-L3-diaminopropane, N-heptacosyl-1,3-dianiinopropane,N-octacosyL 1,3-diaminopropane, N-non'acosyl-L3 diaminopropane,N-triacontyld,B-diaminopropane, N-hentriacontyl-lfi-diaminopropane,N-dotriacontyl-l,3-diaminopropane, N- tritriacontflal,3-d1iaminopropane,N-tetratriacontylalfidiaminopropane,N-pentatriacontyl-l,3-diaminopropane,Nehexatriacontyl-I,3-diaminopropane, N-heptatriacontyl-1,3-diaminopropane, N-octatriacontyl-l,3 diaminopropane,N-nonatriacontyl-l,3-diaminopropane, N-tetracontyl1,3-diaminopropane,etc. As before, mixtures are available commercially, usually at lowerprices, of suitable compounds in this class and advantageously are usedfor the purpose of the present invention. One such mixture is Duorn en Twhich is N-tallow-1,3-diaminoprod pane and predominates in alkyl groupscontaining 16 to 18 carbon atoms each, although the mixture contains asmall amount of alkyl groups containing 14 carbon atoms each. Anothermixture available commercially is N-coco-1,3-diaminopropane whichcontains alkyl groups predominating in 12 to 14 carbon atoms each. Stillanother example is 1 I-soya-1,3-diaminopropane which predominates'inalkyl groups conta ning 18 carbon atoms per group, although it containsa small amount of alkyl groups having 16 carbon atoms.

Wlnle the N-alkyl-1,3-diaminopropanes are preferred compounds of thisclass, it is understood that suitable N-alkyl ethylene diamines, l-alkyl-l,3-diaminobutanes, N-alkyl-1,4-diaminobutanes, N-alkyl-1,3diaminopentanes, N-alkyl-l,4-diaminopentanes,N-alkyl-LS-diaminopentanes, N alkyl 1,3-diaminohexanes,N-alkyl-1,4-diaminohexanes, N-alkyl-l,S-diaminohexanes, N-alkyl-l,6-diaminohexanes, etc. may be employed but not neces sarily withequivalent results. Also, it is understood that polyamines contaim'ng 3or more nitrogen atoms may be employed provided they meet therequirements'hereinbefore set forth. Illustrative examples of suchcompounds include N-dodecyl-diethylene triamine, N-triw decyl-diethylenetriamine, N-tetradecyl-diethylene triamine, etc., N-dodecyl-dipropylanetriamine', N-tridecyl dipropylene triamine, N-tetradecyl-dipropylenetriamine, etc., N-dodecyl-dibutylene triamine, N-tridecyl-dibntylenetriamine, l-tetradecyl-dibutylene triamine, etc., I-dodecyl-triethylenetetramine, ll-tridecyl-triethylene tetramine, N-tetradecyl-triethylenetetramine, etc., N-dodecyltripropylene tetramine,N-tridecyl-tripropylene tetramine, N-tetradecyl-tripropylene tetramine,etc., N dodecyl-tr'- butylene tetramine, N-tridecyl-tributylenetetramine, N- tetradecyl-tributylene tetramine, etc.,N-dodecyl-tetraethylene pentamine, N-tridecyl-tetraethylene pentamine,N-tetradecyl-tetraethylene pentamine, etc., N-dodecyltetrapropylenepentamine, N-tridecyl-tetrapropylene pentamine,N-tetradecyl-tetrapropylene pentamine, etc., N-

dodecyl-tetrabutylene pentarnine, N-tridecyl-tetrabutylene pentarnine,N-tetradecyl-tetrabutylene pentamine, etc.

In another embodiment, polyaminoalkanes meeting the requirementshereinbefore set forth, may be employed but generally such materials arenot available commercially, and, therefore, generally are not preferred.Illustrative examples of such compounds include 1,12-diaminododecane,1,13-diaminotridecane, 1,14-diaminotetradecane, etc;

In general, it is preferred that the amine compound is a saturatedcompound and does not contain double bonds in the chain. However, insome cases, unsaturated compounds may be employed, provided they meetthe other requirements hereinbefore set forth, although not necessarilywith equivalent results. Such amine compounds may be prepared fromunsaturated fatty acids and, therefore, may be available commercially-atlower cost. Illustrative examples of such amine compounds includedodecylenic amine, didodecylenic amine, N-dodecylenic ethylene diamine,N-dodecylenic-1,3-diaminopropane, oleic amine, dioleic amine, N-oleicethylene diamine, N- oleic 1,3 diaminopropane, linoleic amine,dilinoleic amine, N-linoleic ethylene diamine, N-linoleic-1,3-diaminopropane, etc. It is understood that these amine compounds areincluded in the present specifications and claims by reference to amineor amine compounds.

In another embodiment of the invention, two different amines may bereacted With the epihalohydrin compound. At least one of the amines mustmeet the qualifications hereinbefore set forth. The other amine maycomprise any suitable compound containing primary and/or secondary aminegroups. Preferred compounds comprise ethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, etc., similarpropylene and polypropylene polyamines, butylene and polybutylenepolyamines, etc. In still another embodiment, other suitablenitrogen-containing compounds may be used as, for example, urea,monoethanol amine, etc.

As hereinbefore set forth, the amine compound is reacted with anepihalohydrin compound. Epichlorohydrin is preferred. Otherepichlorohydrin compounds include 1,2-epi-4-chlorobutane,2,3-epi-4-chlorobutane, 1,2-epi-5-chloropentane,2,3'epi-5-chloropentane, etc. in general, the chloro derivatives arepreferred, although it is understood that the corresponding bromo andiodo compounds may be employed. In some cases epidihalohydrin compoundsmay be utilized. it is understood that the different epihalohydrincompounds are not necessarily equivalent in the same or differentsubstrate and that, as hereinbefore set forth epichlorohydrin ispreferred.

In general, 1 or 2 mols of amine compound are reacted with l or 2 molsof epihalohydrin compound. It is understood that, in some cases, anexcess of amine or of epihalohydrin may be supplied to the reaction zonein order to insure complete reaction, the excess being removedsubsequently in any suitable manner. When 2 mols of amine are reactedper mol of epihalohydrin con.- pound, the amine may comprise the same ordifferent amine compound.

In a preferred embodiment of the invention, the reaction of 1 mol ofamine compound with 1 mol of epihalohydrin compound proceeds to theformation of polymeric reaction product. In this embodiment of theinvention, the reaction is first effected at a temperature Within therange hereinafter set forth, with only a portion of the reactants beingpresent in the reaction mixture. After the initial reaction iscompleted, the remaining reactants are supplied to the reaction mixtureand the reaction is completed at a higher temperature but within thesame range set forth herein. For example, a portion of the amine may befirst reacted with the epihalohydrin and then the remaining portion ofthe amine is reacted. These polymers may contain from about 3 to about20 or more recurring units and preferably from about 5 to aboutrecurring units.

The desired quantity of alkyl amine and epihalohydrin compounds may besupplied to the reaction zone and therein reacted, although generally itis preferred to supply one reactant to the reaction zone and thenintroduce the other reactant step-wise. Thus, usually it is preferred tosupply the amine to the reaction zone and to add the epihalohydrincompound step-Wise, with stirring. When it is desired to react twodifferent alkyl amines with the epihalohydrin compound, theepihalohydrin compound is supplied to the reaction zone. One of theamines is added gradually, and the reaction completed, followed by theaddition of the second alkyl amine. Generally, it is preferred toutilize a solvent and, in the preferred embodiment, a solution of theamine in a solvent and a separate solution of the epihalohydrin compoundin a solvent are prepared, and these solutions then are commingled inthe manner hereinbefore set forth. Any suitable solvent may be employed,a particularly suitable solvent comprising an alcohol including ethanol,propanol, butanol, etc., 2-propanol being particularly desirable.

The reaction is effected at any suitable temperature, which generallywill be Within the range of from about 20 to about 100 C. and preferablyis Within the range of from about 50 to about 75 C. A higher temperaturerange of from about 30 to about 150 C. or more, and preferably of fromabout 50 to about 100 C., is specified when the reaction is effected atsuperatrnospheric pressure to increase the reaction velocity.Conveniently, this reaction is efiected by heating the amine solution indilute alcohol at refluxing conditions, with stirring, gradually addingthe epihalohydrin compound thereto, and continuing the heating until thereaction is completed.

Either before or after removal of the reaction product from the reactionzone, the product is treated to remove halogen, generally in the form ofan inorganic halide salt as, for example, the hydrogen halide salt. Thismay be effected in any suitable manner and generally is acccmplished byreacting the product with a strong inorganic base such as sodiumhydroxide, potassium hydroxide, etc., to form the corresponding metalhalide. The reaction to form the metal halide generally is elfectedunder the same conditions as hereinbefore set forth. After this reactionis completed, the metal halide is removed in any suitable manner,including filtering, centrifugal separation, etc. It is understood thatthe reaction product also is heated sur'iiciently to remove alcohol andwater and this may be efiected either before or after the treatment toremove the inorganic halide.

In still another embodiment, after the reaction product of an alkylamine and epihalohydrin is prepared, the reaction product may be reactedwith other nitrogencontaining compounds including, for example, alkanolamines, urea, etc., instead of with the same or different alkyl amine ashereinbefore described. Illustrative alkanol amines include ethanolamine, propanol amine, butanol amine, pentanol amine, hexanol amine,etc.

As hereinbefore set forth, a carboxylic acid salt of the condensationproduct prepared in the above manner is used as an additive tohydrocarbon oil. Any suitable carboxylic acid may be utilized in formingthe salt and preferably comprises a dibasic carboxylic acid containingat least 6 and preferably at lease 10 carbon atoms per molecule, andmore particularly from about 20 to about 50 carbon atoms per molecule.The preferred acids are referred to herein as high molecular weightpolybasic carboxylic acids and include adipic, pimelic, suberic,azelaic, sebacic, phthalic, etc., aconitic, citric, etc., hemimellitic,trimesic, prehnitic, mellophanic, pyromellitic, mellitic, etc., andhigher molecular polybasic carboxylic acids. It is understood that amixture of acids may be employed.

A particularly preferred acid comprises a mixed byproduct acid beingmarketed commercially under the trade name of VR1 Acid. This acid is amixture of polybas-ic acids, predominantly dibasic, has an averagemolecular Weight by basic titration of about 750, an average molecularWeight of about 1000, is a liquid at 77 F., has an acid number of aboutand iodine of about 36, and contains about 37 carbon atoms per molecule.

Another particularly preferred acid comprises a mixed acid beingmarketed commercially under the trade name of Empol 1022. This dimeracid is a dilinoleic acid and is represented by the following generalformula:

This acid is a viscous liquid, having an apparent molecular weight ofapproximately 600. It has an acid value of -192, an iodine value of 8O9S, a saponification value of -195, a neutralization equivalent of290-310, a refractive index at 25 C. of 1.4919, a specific gravity atl5.5 C./15.5 C. of 0.95, a flash point of 530 F., a fire point of 600F., and a viscosity at 109 C. of 100 centistokes.

As hereinbefore set forth, dibasic acids containing at least 6 carbonatoms per molecule are preferred. However, it is understood that dibasicacids containing less than 6 carbon atoms also may be employed in somecases and thus include oxalic, malonic, succinic, glutaric, etc.Similarly nonobasic carboxylic acids may be used in forming the salt insome cases and thus include formic, acetic, propionic, butyric, valeric,trimethylacetic, but preferably contains at least 6 carbon atomsincluding caproic, caprylic, lauric, myristic, palmi-tic, stearic,arachidic behenic, lignoceric, cerotic, etc., decylenic, dodecylenic,palmitoleic, oleic, ricinoleic, petroselinic, vaccenic, linoleic,linolenic, eleostearic, licanic, parinaric, gadoleic, arachidonic,cetoleic, erucic, selacholeic, etc.

It is understood that the various acids which may be used in preparingthe salt are not necessarily equivalent and also that mixtures of acidsmay be employed in preparing the salts.

The salt of the carboxylic acid and epihal-ohydrinv amine condensationproduct may be prepared in any suitable manner and may comprise theacid, neutral or basic salt. When utilizing a dibasic acid in formingthe salt, the acid salt generally is preferred, although the neutralsalt may be desirable in some cases. When using a monobasic carboxylicacid in forming the salt, the neutral or basic salt in general ispreferred. The neutral salt is formed by using the reactants in aproportion to give an equivalent number of amine groups and anequivalent number of carboxylic acid groups. Thus, when using amonocarboxylic acid, one mol proportion of the carboxylic acid is usedper each amine group in the condensation product. When using adicarboxylic acid, one mol proportion of the acid per amine group in thecondensation product produces an acid salt. Therefore, when using adicarboxylic acid and a neutral salt is desired, one-half mol,proportion of the acid is used per each amine group in the condensationproduct. In some cases an excess of acid or condensation product may bepresent in the product but generally is not preferred.

The salt may be prepared in any suitable manner and, in general, isreadily prepared by mixing the acid and condensation product at ambienttemperature, preferably with vigorous stirring. While the salt isreadily prepared at room temperature, in some cases it is of advantageto heat the mixture at slightly elevated temperature which generallywill not exceed about 200 F. Excessive temperatures must not be used inorder not to cause formation of esters, amides or other undesiredreaction products. Depending upon the particular condensation productand acid employed, it may be desirable to utilize a solvent,

either in forming a more fluid mixture or the condensation productand/or acid before mixing or during the mixing thereof. Any suitablesolvent may be employed and preferably is an aromatic hydrocarbonincluding benzene, toluene, xylene, ethylbenze'ne, cumene, etc, ormixtures thereof. In other cases the solvent may be selected fromalcohols, ethers, ketones, etc. In many cases it is desired to marketthe salt as a solution in a suitable solvent and conveniently the samesolvent is used during manufacture of the salt as is desired in thefinal product.

It is understood that the different salts which may be prepared and usedin accordance with the'present invention are not necessarily equivalent.F or example, one salt may be effective for a certain purpose in onehydrocarbon -oil,- while another salt may be effective in the samesubstrate for a diiferent purpose or indifferent substrates for the sameor different purposes.

The concentration of salt to be incorporated in the hydrocarbon oil willdepend upon the particular use. For example, when utilized to preventheat exchanger deposits, the salt generally is used in a concentrationof from 1 to 1000 parts per million by weight of the hydrocarbon oil.When used for other purposes, the salt may be used in a concentration offrom about 0.000l% to about 1% or more by weight of the hydrocarbon oil.It is understood that the salt is incorporated in the hydrocarbon oil inany suitable manner and generally is effected with stirring in order toobtain intimate mixing thereof. However, when introduced in a flowingstream of oil, mixing is accomplished by turbulence normally encounteredtherein.

As hercinbefore set forth, the salt is particularly advan-. tageous foruse to prevent deposit formation in heat exchangers. I Such heatexchange is utilized, for example,

' in a hydrotreating process in which oil is subjected to hydrogentreating in the presence of a catalyst comprising alumina-molybdenumoxide-cobalt oxide or alum-inamolybdenum sulfide-cobaltsulfide. The oil,which may comprise gasoline, kerosene, gas 'oil or mixtures thereof, isintroduced intothe process at a temperature of from about ambient to 200F. and is passed in heat exchange with reactor effluent products beingwithdrawn at a temperature of from about 500 to about 800 F. The chargeis heated by such heat exchange to a temperature of from about 300 toabout 600 F., then is heated in a furnace or otherwise to a tempertureof from about 625 to about 800 F. and passed with hydrogen in contactwith the catalyst. This treatment serves to removeirnpurities and tohydrogenate unsaturates contained in the charge. An-' other illustrationis a reforming pnoces in which gasoline is contacted with hydrogen inthe presence of a platinumcontaining catalyst at a temperature of fromabout 700 to about 1000 F. and the hot effluent product from thereaction zone is passed in contact with the charge in order to cool theformer and heat the latter.

An example in which oil is subjected to fractionation and the charge ispassed in heat exchange with the hot eiiluent products is in a crudecolumn. In this column, crude oil is subjected to distillation at atemperature of from about 600 to about 700 F. in order to remove lightercomponents as overhead and/or side streams. In some cases the chargefirst is passed in heat exchange with the overhead and/or side streamsfrom this column and then is passed in heat exchange with the hotterproducts withdrawn from the bottom of the crude column. In this way thecharge is progressively heated and the hotter products are cooled.

The above examples are illustrative of typical uses of heat exchange toefiect economies in the process. However, diliiculty is experienced inthe heat exchange due to deposit formation, with the consequentnecessity of interrupting plant operation as hereinbefore set forth. inaccordance with the present invention, deposit forma tion in heatexchanger is reduced to'an extent that normal plant operation need notbe interrupted for this reason.

' equipment. In general, this equipment comprises a series of tubes or atube coil positioned within a shell. One of the fluids is passed throughthe tubes, while the other fluid is passed through the shell. The heatexchange equipment generally is positioned externally to a frat:-tionatcr or reactor. However, in some cases, the heat exchanger takesthe form of a reboiler or condenser, and either a tube coil or a shellcontaining tubes is positioned within the lower or upper portion of thefractionator or reactor.

When the salt of the present invention is added to a finished product,it is incorporated therein with suitable mixing, and may be used alongwith other additives to be added to the oil for specific reasons as, forexample, metal deactivator, antioxidant, synergist, cetane improver,etc. As hereinbefore set forth, the salt serves to improve the oil inmany ways including preventing deposition of sediment, preventingformation of varnish and sludge, preventing corrosion of metal surfaces,depressing pour point, preventing icing, etc. It is understood that allof these improvements are not necessarily obtained in all substrateswith the same additive. However, the diflerent oils will beimproved inone or more ways as hereinbefore set forth.

The following examples are introduced to illustrate further the noveltyand utility of the present invention but not with the intention ofunduly limiting the same.

The reaction was efiected by first forming a solution of 2 mols ofepichlorohydrin in 600 cc. of a solvent mixture comprising 400 cc. ofxylene and 200 cc. of 2propanol. A separate solution of 2 mols o1":Armeen HTD was prepared in an equal volume of xylene. One mol of thelatter solution was added gradually to the epichlorohydrin solution,with stirring and heating at 55 60 C. for a period of 2.5 hours. Thenanother mol of Armeen HTD was added gradually to the reaction mixture,stirred and reacted at 80 C. for 2.5 hours. One mol of sodium hydroxidethen was added with stirring and heating at 85- 90 C. for 3.5 hours,after which another mol of sodium hydroxide was added and the mixturestirred and reacted at 85 -90 C. for one hour. Following completion ofthe reaction, the mixture was cooled, filtered, and the filtrate thenwas distilled to remove the alcohol. The product was recovered as a 50%by weight solution of active ingredient in xylene.

10.04 grams of the 50% solution of the condensation product prepared inthe manner described above was mixed with 11.6 grams of VR-l acid. Ashereinbefore set forth, VR-l acid is a dibasic acid containing about 37carbon atoms per molecule. 11.6 grams of xylene was added to the mixtureso that a final solution of 0% active ingredient was prepared. Themixing was effected at room temperature with stirring, following whichthe mixture was heated at 140 F. for one hour on a water bath. Theproduct was recovered as a viscous, dark brown liquid and is an acidsalt because two equivalents of carboxylic acid groups were used pereach amine group in the condensation product.

Example 11 A salt prepared in the manner described in Example I wasevaluated as a corrosion inhibitor. In this evaluation, which is amodified M.I.L.1.250l7 procedure, 300 cc. of depolarized isooctane, towhich 30 cc. of synthetic sea water is added, is placed in a beaker opento the atmosphere. A steel strip of thickness and V8" wide is welded toa similar strip enclosed in a glass tube. The probe then is suspended inthe mixed oilwater suspension, heated to and maintained at 100 F. for 20hours. The extent of corrosion is determined by measuring the loss inconductivity which in turn is converted to loss of steel, reported asmicro inches penetration. When a blank or control sample of theoil-water emulsion is evaluated in the above manner, the corrosion isreported as about 150 micro inches penetration. In contrast, in anotherevaluation in which 60 parts per million of the salt described inExample I was incorporated in the oil-water suspension, the corrosionwas only 13 micro inches penetration.

From the above data it is seen that the salt of the present inventionwas very efiective in retarding corrosion.

Example III A salt prepared in the manner described in Example I alsowas evaluated as a corrosion inhibitor by a different method. Thismethod is known as the humidity cabinet test. In this test, a highlypolished steel panel is dipped into a viscous naphthenic mineral oil,excess oil is drained, and the panel is placed in a humidity cabinetmaintained at 120 F. in an atmosphere saturated with water. The panelsare rotated slowly, and the days required for visible corrosion toappear on the panel is reported. A panel dipped in a control sample ofthe oil (not containing this additive) undergoes visible corrosion in2-3 hours.

1% by weight of a salt prepared in the manner described in Example I wasincorporated in another sample of the oil. The panel dipped in this oiland then placed in the humidity cabinet did not undergo visiblecorrosion until after 768 hours of exposure at 120 F. to the atmospheresaturated With water. Thus, it will be seen that this additive served toconsiderably reduce corrosion.

Example IV The salt of this example is the oleic acid salt of thecondensation product of epichlorohydrin and tallow amine. Thiscondensation was eifected in substantially the same manner as describedin Example I. The salt was prepared by mixing 100.2 grams of the 50% bypoint of 10 F.

weight solution of the condensation product in xylene with 41 grams ofoleic acid and 41 grams of xylene. The mixture Was stirred and heated at124 F. for 30 minutes. The product was a neutral salt, was recovered asa 50% solution of active ingredient, and was a slightly viscous, reddishbrown liquid.

Example V The salt prepared in the manner described in Example IV isused as a pour point depressant in lubricating oil. The lubricating oilis a commercial S.A.E. 20 Mid- Continent solvent extracted oil which,without additive, has an ASTM cold test of 5 F. and an ASTM pour 1% byweight of the salt prepared as described in Example III is incorporatedin a sample of this lubricating oil and serves to reduce the ASTM coldtest and the ASTM pour point.

Example VI A salt prepared in substantially the same manner as describedin Example I is evaluated in a method referred to as the Erdco test. Inthis method, heated oil is passed through a filter, and the timerequired to develop a diiferential pressure across the filter of 25 in.Hg is determined. It is apparent that the longer the time, the moreeffective is the additive. However, with a very effective additive, thetime to reach a differential pressure across the filter of 25 in. Hg islengthened beyond reasonable limits that the test is stopped after about300 minutes and the differential pressure at that time is reported.

The oil used in this example is a commercial I.P.-6 jet fuel. Whenevaluated for use as a jet fuel, which normally encounters highertemperature, the test is run at a higher temperature. The preheater isrun at a temperature of 400 F. and the filter is run at a temperature of500 F. The jet fuel, without additive, developed a differential pressureacross the filter of 25 in. Hg in 60 minutes. The salt prepared in themanner described in Example I is added in a concentration of 0.005% byweight to another sample of the jet fuel and serves to considerablylengthen the time before a differential pressure of 25 in. Hg isreached.

Example VII A salt prepared in substantially the same manner asdescribed in Example I is also evaluated according to the C.F.R. fuelcoker thermal stability test. In this test, the oil heated to thespecified temperature is passed through the annular space surrounding aheated inside tube of 17" length and A2" diameter positioned Within anoutside tube of inside diameter. The inside tube is heated by means of aheating coil positioned therein to a temperature of either 300 or 400 F.depending upon the particular fuel being evaluated. The test isconducted for 300 minutes, at a pressure of pounds per square inch, anda flow rate of 6 pounds of fuel per hour. Following the run theequipment is dismantled, 13" or less of the inner tube is marked off in1" increments and the deposits on the outside surface of the heatedinner tube are rated by visual comparison with standard metal coupons.In general the rating is substantially as follows:

0 clean and bright 1 metal dulled but not discolored 2 light yellowdiscoloration 3 yellow to tan discoloration 4 anything darker or heavierthan 3 The ratings for the individual 1" increments are added togetherto give a final tube rating. Military specifications for jet fuelsrequire that none of .the 1" increments rates poorer than 3.

The fuel evaluated in this example is a LR-6 commercial fuel and wastested at 400 F. A sample of the jet fuel evaluated in the above mannerhad a tube rating 1 1 of 15. 50 parts per million by weight of the saltdescribed above is incorporated in another sample of this fuel and, whenevaluated in the above manner, will considerably lower the tube rating.

Example VIII with reactor efliuent being withdrawn at atemperature ofabout 675 F. This serves to heat the charge to a temperature of about550 F. and to cool the reactor effiuent to a temperature of about 325 F.In this unit the charge is passed through the tubes of the exchanger andthe reactor effluent is passed through the shell. '25 parts per millionby Weight of the salt is incorporated in the gasoline before the same ispassed into the exchanger and this serves to prevent heat exchangerdeposits and to permit extended use of the heat exchanger withoutrequiring shutting down the plant because of the plugging of the heatexchanger tubes.

I claim as my invention:

1. A salt of a oarboxylic acid of from about 6 to about 50 carbon atomsper molecule and of the condensation product of from 1 to 2 mols of anepihalohydrin compound with from 1 to 2 mols of an aliphatic amine offrom about 12 to about 40 carbon atoms, said salt being the reactionproduct offrom 1 to 2 mol proportions of acid per 1 to 2 mol proportionsof amine group in the condensation product.

2. A salt of a polybasic carboxylic acid of from about 6 to about 50carbon atoms per molecule and of the con densation product of from 1 to2 mols of an epihalohydrin compound with from 1 to 2 mols of an alkylamine of from about 12 to about 40 carbon atoms, said salt being thereaction product of from 1 to 2 mol proportions of acid per 1 to 2 molproportions of amine group in the V condensation product. a

3. -A salt of a dibasic carboxylic acid of from'about 6 to about 50carbon atoms per molecule and of the con densation product of from 1 to2 mols of epichlorohydrin With from 1 to 2 mols of an alkyl amine offrom about 12 to about 40 carbon atoms, said salt being the reactionproduct of from 1 to 2 mol proportions of acid per 1 to 2 molproportions of amine group in the condensation product,

4. A salt of a di-basic carboxylic acid containing'from about 20 toabout carbon atoms per molecule and ofthe condensation product of from 1to 2 mols of epichlorohydrin with from 1 to 2 mols mallow amine, saidsalt being the reaction product of froml to 2 mol proportions'of acidper 1 to 2 mol'proportions of amine group in the condensation product.

5. A salt of a monobasic carboxylic acid containing from about 6 toabout '50 carbon atoms per molecule and of the condensation product offrom 1 to 2 mols of epichlorohydrin with from 1 to 2 mols of an alkylamine having from about 12 to about 40 carbon atoms per molecule, saidsalt being the'reaction product of from 1 to 2 mol proportions of acidper 1 to 2 mol proportions of amine group in the condensation product.

6. An oleic acid salt of the condensation product of from 1 to 2 mols ofepichlorohydrin with from 1 to 2 mols of talloW amine, said salt beingthe reaction product of from 1 to 2 mol proportions of acid per 1 to 2mol proportions of amine group in the condensation product.

References Cited in the file of this patent UNITED STATES PATENTS

1. A SALT OF A CARBOXYLIC ACID OF FROM ABOUT 6 TO ABOUT 50 CARBON ATOMSPER MOLECULE AND OF THE CONDENSATION PRODUCT OF FROM 1 TO 7 MOLS OF ANEPIHALOHYDRIN COMPOUND WITH FROM 1 TO 2 MOLS OF AN ALIPHATIC AMINE OFFROM ABOUT 12 TO ABOUT 40 CARBON ATOMS, SAID SALT BEING THE REACTIONPRODUCT OF FROM 1 TO 2 MOL PROPORTIONS OF ACID PER 1 TO 2 MOLPROPORTIONS OF AMINE GROUP IN THE CONDENSATION PRODUCT.